US9447245B2 - Cross-linking and stabilization of organic metal complexes in networks - Google Patents

Cross-linking and stabilization of organic metal complexes in networks Download PDF

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US9447245B2
US9447245B2 US14/131,594 US201214131594A US9447245B2 US 9447245 B2 US9447245 B2 US 9447245B2 US 201214131594 A US201214131594 A US 201214131594A US 9447245 B2 US9447245 B2 US 9447245B2
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Thomas Baumann
Tobias Grab
Michael Bächle
Daniel Volz
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Samsung Display Co Ltd
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Definitions

  • the invention relates to organic transition metal complexes and their cross-linking into a multi-dimensional network.
  • the invention relates to a method for the production of an organic transition metal complex, which is cross-linked in a multi-dimensional network by formation of covalent bonds.
  • transition metal complexes Due to their properties, phosphorescent transition metal complexes become more and more important as highly efficient emitters in optoelectronic components such as OLEDs.
  • the spin-orbit coupling induced by the transition metal atom results in an increased intersystem-crossing rate from the excited singlet state to the triplet state and thus in the use of the singlet excitons as well as the triplet excitons for emission and thereby allows a theoretical achievable internal quantum yield of 100%.
  • phosphorescent dyes are usually introduced into appropriate energetically adjusted host materials.
  • Polymeric structures are particularly suitable for this purpose due to the ease of processing by liquid processing from solution. Ideally, these should fulfill additional functions such as the spatial separation of the dye molecules to prevent undesirable concentration quenching processes and triplet-triplet-annihilation under emission reduction, increased charge carrier injection and transport and an increased recombination probability directly on the emitter molecules.
  • the combination of suitable polymeric host structures with appropriate statistically blended emitter compounds and additionally inserted charge transport molecules represents a method diversely used for the preparation of polymeric light emitting diodes (PLEDs).
  • PLEDs polymeric light emitting diodes
  • the OLED components produced this way have mostly high efficiencies, these mixed systems can be subject to undesired phase separations, aggregations or crystallization processes, which have a negative effect on the capacity and the lifetime of the components. Therefore, the production of adapted (co)polymers, which fulfill different functions such as charge transport and emission while at the same time using the advantages of liquid processing, is of steadily increasing interest.
  • the first strategy allows a modular design with the basic attachment of a large amount of different metal complexes to the polymer and has as an advantage the extensive and more detailed analysis of the metal-free polymers synthesized before by common polymer analysis such as, for example, GPC and NMR. Additionally, the amount of metal complex in the final polymer can theoretically be varied by careful adjustment of the potential coordination sites. The use of functionalization methods orthogonal to the actual polymerization reactions, which also have to proceed in high yields, is necessary for the success of the modular post-polymerization method.
  • the advantage of the second route consists of the controlled structure and quantitative functionalization of the metal complexes by using common polymerization methods, which in part must be adjusted to the correspondent metal complex-functionalized monomers and whose accurate characterization by common analytical methods is not possible in most cases due to the attached metal complexes.
  • the cross-linked films show high solvents resistance and very good properties for the formation of films, making the principle preparation of multi-layer systems by sequential liquid processing of different layers possible.
  • this approach represents no controlled build-up of well-defined metal complex-functionalized polymers since the polymerization proceeds only by thermal processes and completely uncontrolled. It is, for example, not possible to exactly adjust by controlled polymerization methods the molecular weight, the chain length, and the polydispersity of the polymer to operate reproducibly and to make adjustments according to the requirements of a standardized liquid-processing.
  • FIG. 1 shows the general scheme for the linkage of organic metal complexes (first reactant) with monomers, oligomers or polymers (second reactant), each carrying a corresponding anchor group which enables the cross-linking of the organic metal complex in accordance with an embodiment of the present invention.
  • FIG. 2 shows selected examples of anchor groups of a first and a second anchor group species (each arranged in rows) in accordance with an embodiment of the present invention.
  • FIG. 3 shows an example reaction for the linking of an alkene substituted copper complex with a polymeric azide as second reactant in accordance with an embodiment of the present invention.
  • FIG. 4 shows a histogram of the AFM-picture before and after rinsing with xylene (see example 3) in accordance with an embodiment of the present invention.
  • FIG. 5 shows the photoluminescence spectra of the compounds 9.2 A, 9.2 B and 9.2 C powder measurement, room temperature, under normal atmosphere) in accordance with an embodiment of the present invention.
  • the invention in a first aspect, relates to a method for the preparation of an organic transition metal complex cross-linked into a—preferably insoluble—multi-dimensional network.
  • This method comprises the performance of a first reaction, which comprises the reaction of a first reactant in the form of an organic metal complex with a second reactant (different to the first reactant).
  • the second reactant serves for the formation of a multi-dimensional network.
  • the metal complex is being cross-linked into a multi-dimensional network by the formation of covalent bonds, i.e. at least two bonds of the ligand of the transition metal complex with the multi-dimensional network resulting from the second reactant are formed.
  • This can be in its simplest shape a ladder-like (two-dimensional) structure, in which two network strings are linked by at least one transition metal complex, which forms via at least one ligand with one of the strings each at least one covalent bond.
  • Covalent hereby means the bonding between nonmetal elements.
  • complicated three-dimensional networks are possible, which comprise metal complexes cross-linked with a variable number of network strings. The cross-linked metal complex is thus immobilized in the multi-dimensional network.
  • the transition metal complex comprises at least two anchor groups of a first anchor group species, which serve for the covalent binding of together at least two ligands of the transition metal complex into the multi-dimensional network.
  • the second reactant comprises at least one anchor group of a second anchor group species, which is suitable for the binding of the second reactant to the first anchor group of the transition metal complex.
  • the cross-linking of the transition metal complex into the multi-dimensional network is carried out by a reaction of the at least two anchor groups of the transition metal complex with one second anchor group each of a second reactant.
  • a third reactant which can also be named “spacer” molecule, takes part in the first reaction.
  • the transition metal complex comprises at least two anchor groups of a first anchor group species, which is suitable for the covalent integration together at least two ligands of the transition metal complex into the matrix by a second anchor group.
  • the second reactant comprises an anchor group of a first anchor group species, which serves for the binding of the second reactant to a second anchor group, so that the transition metal complex cannot bind directly to the second reactant.
  • a third reactant is added, which comprises two anchor groups of a second anchor group species, wherein each of these anchor groups of the third reactant can form a covalent bond with one first anchor group each (namely of the transition metal complex and of the second reactant).
  • the third reactant (“spacer” molecule) can be, for example, an alkyl chain of a desired chain length that comprises at two molecule parts spaced apart from each other, e.g. at ends opposite to each other, one anchor group each, which mediates the binding to the transition metal complex or to the second reactant.
  • alkyl chains aryl, heteroaryl, alkenyl, alkinyl, trialkylsilyl and triarylsilyl groups and substituted alkyl, aryl, heteroaryl and alkenyl groups, optionally with substituents such as halogens, lower alkyl groups and/or electron donating and withdrawing groups, as well as common charge transport units such as, for example, arylamines, carbazoles, benzimidazoles, oxadiazoles etc. are also possible.
  • the substituents can also lead to annulated ring systems.
  • the metal complex and the second reactant are soluble in a common organic solvent (in particular for the production of OLED components).
  • common organic solvents include ethers, alkanes as well as halogenated aliphatic and aromatic hydrocarbons and alkylated aromatic hydrocarbons, especially toluene, chlorobenzene, dichlorobenzene, mesitylene, xylene and tetrahydrofuran.
  • the formed multi-dimensional network with cross-linked organic metal complexes is insoluble, which particularly makes the formation of a structure of several overlapping layers of such a multi-dimensional network possible in a simple manner.
  • the first and the second anchor group may in particular be selected from the group of chemical groups shown in FIG. 2 . If the metal complex is an emitter, the anchor group is preferably not conjugated to the emitter system in order not to affect the emission of the complex.
  • any organic transition metal complex which carries at least one of its ligands a first anchor group, but no main group metal or semi-metal, can be used in the method.
  • the metal complex comprises at least one metal center and at least one organic ligand.
  • the metal complex can be mononuclear or polynuclear (di-, tri-, tetranuclear, etc.) and can carry one or several ligands.
  • the ligands can be mono- or polydentate. If a mononuclear complex carries only one ligand, this ligand is polydentate. If the complex is not neutral, a corresponding counter ion has to be provided, which preferably does not take part in the first reaction as described herein.
  • the ligands at the metal center are not exchanged or replaced by other ligands.
  • the occurring reaction takes place exclusively directly at the ligand or in the ligand sphere, the basic structure of the metal complex remains unchanged.
  • the occurring reaction involves a covalent cross-linking, wherein the resulting new covalent bonds are preferably formed between non-metal elements.
  • Preferred organic metal complexes are, for example, light emitters, which can be applied in optoelectronic components, such as OLEDs.
  • Another group of preferred metal complexes are semiconductors. Such emitting and semiconducting metal complexes are known in the art.
  • At least one ligand of the metal complex comprises a first anchor group.
  • a metal complex comprises two anchor groups, preferably of one anchor group species, which can be arranged at one ligand or are preferably distributed to two ligands of the metal complex.
  • several ligands of a metal complex comprise one or several anchor groups, wherein the number of anchor groups at the metal complex and at the second ligand determines the degree of cross-linking.
  • the multi-dimensional network is a two-dimensional or three-dimensional network.
  • a three-dimensional network is preferred.
  • the second reactant used in the method can be selected from a group consisting of a monomer, a oligomer and a polymer.
  • Low-molecular, reactive molecules are here referred to as monomers, which can react to molecular chains or networks, to unbranched or branched polymers. Examples are common monomers such as styrene, ethylene, propylene, vinylchloride, tetrafluoro ethylene, acrylic acid methylester, methacrylic acid methylester, bisphenol A/phosgene, ethylene glycols, terephthalic acids and organochloro silanes.
  • a molecule which is composed of 2 to 30 structurally identical or similar units is referred to as oligomer herein.
  • oligomers are oligoethylene, oligopropylene, oligovinylchloride, oligotetrafluoro ethylene, oligoacrylic acid methylester, oligomethacrylic acid methylester, oligocarbonates, oligoethylene glycol, oligoethylene terephthalate, oligo(organo)siloxanes.
  • Polymers are molecules that are composed of more than 30 structural identical or similar units.
  • polymers examples include polystyrene, polyethylene, polypropylene, polyvinylchloride, polytetrafluoro ethylene, polyacrylic acid methylester, polymethacrylic acid methylester, polycarbonates, polyethylene glycol, polyethylene terephthalate, and poly(organo)siloxanes.
  • monomer includes in one embodiment lower molecular compounds, such as for example phosphoalkanes, phosphazenes, ferrocenylsilanes, and ferrocenylphosphines.
  • cross-linking of a metal complex described herein has to be distinguished from the insertion of a complex into a polymer, wherein the complex is bound to one polymer string each and thus only the solubility characteristics of the attached complex change. Furthermore, to date, cross-linking is only known between polymers, which are not bound to metal complexes, wherein the polymers always react in a cross-linking reaction with themselves, thus are only homo-cross-linked. In contrast, according to the invention, cross-linking is only initiated by the formation of a bond to the metal complex, whereby the corresponding polymers are hetero-cross-linked to the metal complex.
  • the invention relates in one embodiment to materials, in particular to liquid-processable optoelectronic materials, which ensure due to their special structure both the covalent binding of a metal complex, for example a highly efficient emitter metal complex, to a functionalized second reactant such as to a monomer, oligomer or polymer, and its cross-linking and thus leading to its insolubility.
  • a metal complex for example a highly efficient emitter metal complex
  • a functionalized second reactant such as to a monomer, oligomer or polymer, and its cross-linking and thus leading to its insolubility.
  • a fourth reactant is used in the first reaction of the method besides the metal complex, the second reactant and optionally the third reactant, wherein the fourth reactant is a hole or electron conducting chemical group and/or a charge blocking chemical group, which can also be cross-linked as a charge transport unit or a charge blocking unit.
  • Examples for hole or electron conducting chemical groups are arylamines such as N,N′-bis(naphthalene-1-yl)-N,N′-bis(phenyl)-benzidine, N,N′-bis(naphthalene-1-yl)-N,N′-bis(phenyl)-2,2′-dimethylbenzidine, carbazoles such as 4,4-bis(carbazole-9-yl)biphenyl, 1,3-bis(carbazole-9-yl)benzene, benzimidazoles such as 1,3,5-tris(1-phenyl-1H-benzo[d]imidazole-2-yl)benzene, oxadiazoles such as 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole, triazoles such as 3-(4-biphenyl)-4-phenyl-5-tert-butylphenyl-1,2,4-
  • the fourth reactant also comprises at least one anchor group of the first and/or the second anchor group species for the binding into the multi-dimensional network, depending whether the fourth reactant shall be bound to the metal complex or to the second reactant.
  • the invention consists in a stabilization and cross-linking method of metal complexes by monomers, oligomers and polymers, which consist of one or several metals and one at least bidentate or several mono- or polydentate ligands.
  • the organic metal complex and the second reactant carry complementary chemical anchors of a (first or second) anchor group species, which are covalently bound to each other in a reaction proceeding as fast and completely as possible.
  • luminescent or semiconducting metal complexes can be immobilized, e.g for applications in organic electronics, in order to increase the lifetime and long-term stability of the correspondent components.
  • the “click chemistry” comprises reactions, which are performable with high yields, are applicable in a broad range of applications, proceed (stereo)specifically, comprise simple reactions conditions (preferably insensitive to water and oxygen), comprise easily removable, as nonhazardous as possible side products and reagents (if at all), proceed in environmentally friendly and/or easily removable solvents such as water or without solvents and/or need a simple purification (extraction, phase separation, distillation or crystallization—preferably no chromatography) or no purification at all.
  • “Click” reactions are in most cases highly thermodynamically favored with often more than 20 kcal mol ⁇ 1 , leading to a single product with fast conversions and high selectivity. In most cases, carbon heteroatom bonds are formed with click reactions.
  • nucleophilic substitutions especially ring opening of tense electrophilic heterocycles such as epoxides and aziridines, carbonyl chemistry of the “non-aldol” type such as the formation of aromatic heterocycles or hydrazones, additions to carbon-carbon double bonds such as the oxidative formation of epoxides and aziridines, dihydroxylation and Michael additions as well as cycloadditions to unsaturated C—C bonds, in particular 1,3-dipolar cycloadditions and Diels-Alder reactions can be applied. Further examples for such reactions are cross-coupling reactions for the formation of C—C bonds such as the Ullmann reaction, the Sonogashira reaction and the Glaser coupling. All of these reactions are known to a person of skill in the art.
  • reactions are relevant which do not need the addition of another reactant (i.e. a reactant other than the first, second and, if applicable, the third and, if applicable, the fourth reactant).
  • a reactant other than the first, second and, if applicable, the third and, if applicable, the fourth reactant examples for such reactions are, besides the 1,3-bipolar cycloadditions and Diels-Alder reactions mentioned above, nitrone-alkyne reactions, nitril oxide-alkyne reactions, thiol-ene reactions, thiol-yne reactions, thiol-isocyanite reactions, tetrazole-alkene reactions and other methods known as click reactions in the chemical literature.
  • the reaction takes place in the presence of a catalyst for the catalysis of the reaction.
  • the catalyst is educt/reactant and at the same time catalyst.
  • the metal complex comprises the catalyst, i.e. the transition metal center contained in the organic metal complex serves also as a catalyst, so that a self-catalyzed cross-linking takes place.
  • the copper-catalyzed click reaction between a terminal or activated alkyne as first anchor group of a first anchor group species and an azide as anchor group of a second anchor group species is shown in FIG. 3 .
  • the catalyst can, for example, be produced in situ from a Cu(II) species.
  • CuSO 4 with sodium ascorbate or Cu(0) as reduction agent can be used, but other stabilized Cu(I) salts and complexes are also possible.
  • the metal complex is a Cu(I) or a Cu(II) complex, so that the reaction takes place self-catalytically.
  • Other possible catalysts are Pt, Pd, Ru, Au and Ag.
  • the reaction between metal complex and second reactant proceeds preferably at a temperature which is higher than room temperature. At least 50° C. are preferred, particularly preferred are temperatures from 80° C. to 120° C.
  • the reaction time needed at the particular reaction temperature can be easily determined by a person skilled in the art. Usually, a reaction time of 1 minute to 60 minutes, preferably of 10 minutes to 30 minutes is to be anticipated, so that the metal complex is immobilized and thus stabilized and insoluble.
  • the thermal activation can also be carried out by exposure to microwaves, whereby the reaction times can be shortened considerably to less than 1 minute.
  • a photochemical activation takes place. This leads in comparison to the thermal activation mostly to shortened reaction periods, which can be less than 1 minute. Therefore, a photochemical activated reaction can also be performed without catalyst. A reaction in the presence of a catalyst is also possible.
  • an anchor group for example an alkyne linker
  • an aromatic azide is used as complementary anchor group
  • the emission colors of such emitting complexes which are based on charge transfer transitions between the metal ions and the ligands, can be influenced.
  • metal complexes with three or more ligands e.g. four, five or six ligands
  • three or more linking positions e.g. four, five or six linking positions
  • the complexes can thereby be linked to the polymers as well as bound to hole or electron conductors (fourth reactants).
  • the optical, mechanical and electrical properties of the obtained substances can thus be influenced by the particular composition of the azide mixture.
  • a second reaction is performed after the first reaction described above.
  • This second reaction comprises a fifth reactant in the form of an organic metal complex and a sixth, preferably soluble reactant for the formation of a preferably insoluble multi-dimensional network, wherein the metal complex is cross-linked during the second reaction in the forming multi-dimensional network by formation of covalent bonds.
  • aspects described for the first reaction apply here analogously.
  • the fifth reactant of the second reaction can be identical to or different from the first reactant of the first reaction.
  • the sixth reactant of the second reaction can be identical to or different from to the second reactant of the first reaction.
  • cross-linking that occurs according to the invention allows for a fast and simple alignment of any number of photoactive layers, whose solubility does not have to be adjusted exactly to each other as in previous systems. This results in a considerable simplification of the processing, since the selection of the individual active layers does no longer have to be orthogonal to each other with regard to solubility, but can be combined almost independently from each other. This allows for the sequential application of any number of different layers and thereby leads to a significant increase of efficiency and durability.
  • the anchor groups of the first and the second anchor group species are present in equimolar amounts, so that all anchor groups can form covalent bonds with complementary anchor groups.
  • the invention relates to an organic metal complex cross-linked into a multi-dimensional network, which is producible by a method described herein.
  • an advantage of the invention is the stabilization of the geometry of the emitter metal complex by the immobilization through cross-linking.
  • the possible movement of the ligands of the metal complexes to each other is highly limited.
  • the complexes are fixed and stabilized.
  • the transition probabilities for non-radiative processes are reduced by rotation and twisting in contrast to “free” complexes:
  • the emission quantum yields of the emitters are increased.
  • the fixation leads to maximal utilization of the energetic gap between the ground state and the first excited state.
  • the invention also improves the efficiency of optoelectronic components: Due to the sterical hindrance of the metal complexes, the overlapping integrals between states not used for emission decrease, the population of rotational and vibrational states become less likely.
  • the stability of the complexes increases due to the prevention of bond breaking and non-radiative relaxations through free mobility of the ligands of a metal emitter system. By means of the immobilization, it is possible to shift the emission of a given free, i.e. not cross-linked, emitting metal complex in the direction to or into the blue spectral range.
  • the invention relates to the use of an organic metal complex cross-linked in a multi-dimensional network as an emitter or an absorber in an optoelectronic component, provided that the metal complex is a light emitter or a light absorber.
  • the invention relates to an optoelectronic component comprising a cross-linked organic metal complex, as described herein.
  • the optoelectronic component can be an organic light-emitting diode (OLEDs), a light-emitting electrochemical cell (LEECs or LECs), OLED sensors, optical temperature sensors, organic solar cells (OSCs), organic field effect transistors, organic diodes, organic photodiodes and “down conversion” systems.
  • OLEDs organic light-emitting diode
  • LEECs or LECs light-emitting electrochemical cell
  • OLED sensors optical temperature sensors
  • organic solar cells (OSCs) organic solar cells
  • organic field effect transistors organic diodes
  • organic photodiodes organic photodiodes and “down conversion” systems.
  • the invention relates to a method for the production of an organic metal complex cross-linked in a multi-dimensional network, in particular to a thin layer with a thickness of 75 nm to 300 nm, in particular 100 nm to 250 nm, particularly for the production of an optoelectronic component.
  • the method comprises at least the following steps: First, a mixture of a first reactant in the form of an organic metal complex and a second reactant, thus a means for the immobilization of the metal complex, is applied to a solid support.
  • the metal complex is cross-linked in the forming multi-dimensional network by formation of covalent bonds during the performed first reaction of the first reactant with the second reactant.
  • the formation of the cross-linking is preferably carried out at higher temperatures, preferably between 80° C. to 120° C.
  • the application of the mixture of both reactants on a solid support can be carried out by means of all methods known in the state of the art, in particular by means of inkjet printing, dipping, spincoating, slot-die coating or knife coating.
  • the invention relates to the use of a cross-linked metal complex as an emitter material for an optoelectronic component, in particular as optoelectronic ink.
  • the invention in a seventh aspect, relates to an organic transition metal complex with at least one transition metal center and at least one ligand.
  • the metal complex comprises two anchor groups of a first anchor group species for the reaction with an anchor group of a second anchor group species for cross-linking, wherein the anchor group of the metal complex can form a covalent bond with the anchor group of a second reactant, which serves for the formation of a multi-dimensional network, during the cross-linking reaction.
  • the invention relates to the use of such a metal complex for the cross-linking and immobilization of the metal complex to a second reactant, which comprises an anchor group of a second anchor group species.
  • the invention relates to a method for the functionalization of an organic metal complex with two anchor groups through which the metal complex is bound to a second reactant carrying a second anchor group and can be immobilized, since the anchor groups of a first anchor group species of the metal complex react with the anchor group of a second anchor group species of the second reactant and can form a covalent bond.
  • reaction product is referred to as composite herein.
  • the anchor groups shown opposite to each other can, bound on the one hand to the metal complex and on the other hand to the second reactant, form a covalent bond between the reactants and thus cross-link and immobilize the metal complex.
  • First and second anchor group species are addressed here as anchor A and anchor B.
  • the anchor A shown here can represent the first or the second anchor group species and the anchor B can represent the second or the first anchor group species, respectively.
  • R1-R6 can each independently be hydrogen, halogen or substituents, which are bound via oxygen (—OR*), nitrogen (—NR* 2 ) or silicon atoms (—SiR* 3 ) as well as alkyl (also branched or cyclic), aryl, heteroaryl, alkenyl, akinyl groups or substituted alkyl (also branched or cyclic), aryl, heteroaryl and alkenyl groups with substituents such as halogens or deuterium, alkyl groups (also branched or cyclic), and further generally known donor and acceptor groups such as, for example, amines, carbonyls, carboxylates and their esters, and CF 3 groups.
  • R1-R6 can optionally also lead to annulated ring systems;
  • R* organic group, selected from the group consisting of: hydrogen, halogen or deuterium, as well as alkyl (also branched or cyclic), aryl, heteroaryl, alkenyl, akinyl groups or substituted alkyl (also branched or cyclic), aryl, heteroaryl and alkenyl groups with substituents such as halogens or deuterium, alkyl groups (also branched or cyclic), and further generally known donor and acceptor groups such as, for example, amines, carboxylates and their esters, and CF 3 groups;
  • X halogen, OSO 2 Me, OSO 2 Tolyl, OSO 2 CF 3 .
  • the ball shown stands for polystyrene but can also represent any other polymer, oligomer or monomer as a second reactant.
  • the heights are normalized to 1, the position of the histograms on the X-axis is arbitrary, but true to scale.
  • the histograms were not arranged on top of each other, but side by side. The processing was carried out at 40° C., the scan-size of the underlying images is 1 ⁇ m 2 .
  • such reactions are preferred which do not need the addition of another reactant besides the metal complex and the second reactant, i.e. reactions that need at the most a catalyst that does not interfere with the further use.
  • examples for such reactions are 1,3-bipolar cycloadditions, Diels-Alder reactions, nitrone-alkyne reactions, nitril oxide-alkyne reactions, thiol-ene reactions, thiol-yne reactions, thiol-isocyanate reactions, tetrazole-alkene reactions and other methods known as click reactions in chemical literature.
  • One example is the copper-catalyzed click reaction between a terminal or activated alkyne and an azide. This reaction provides regioselectively and in high yields and conversions 1,4-triazoles (see FIG. 2 ).
  • Phenylacetylene (103 mg, 1.0 mmol, 1.0 eq.) and benzyl azide (133 mg, 1.0 mmol, 1.0 eq.) were dissolved in an air-tight lockable vial with a septum in 10 mL dry dichloromethane.
  • the Cu complex (catalytic or stoichiometric amounts) shown below was added, the vial sealed and the reaction stirred at room temperature for 2 days.
  • the reaction mixture was put in 50 mL methanol and stirred for 20 min. The complex was removed by filtering and the filtrate was concentrated.
  • the Cu complex (1.341 g, 1.0 mmol, 1.0 eq.) as first reactant was dissolved in an air-tight lockable vial with a septum in 10 mL dry dichloromethane and benzyl azide (466 mg, 3.5 mmol, 3.5 eq.) as second reactant was added.
  • the reaction was stirred at room temperature for 12 hours, filtered over a syringe filter and precipitated by adding dropwise into diethyl ether.
  • the Cu complex (440 mg, 0.33 mmol, 1.0 eq.) was dissolved as first reactant in an air-tight lockable vial with a septum in 10 mL dry dichloromethane and converted with poly-(vinylbenzylazide- ⁇ /t-styrene) (370 mg, 1.0 mmol, 3.0 eq.) as second reactant.
  • the reaction was stirred at room temperature for 12 hours, and the product precipitated as insoluble greenish solid from the reaction solution.
  • the precipitate was withdrawn by suction, washed with 20 mL dichloromethane, 20 mL diethyl ether and 20 mL methanol and dried in high vacuum.
  • the product poly-(4-(2-(1-(4-vinylbenzyl-1H-1,2,3-triazole-4-yl)ethyl)-2-(diphenylphosphino)pyridine)-alt-styrol @ CuI was a light green solid in 66% yield (540 mg, 0.21 mmol) and represents a cross-linked metal complex.
  • the identity of the product was clearly proven by infrared spectroscopy, photoluminescence spectroscopy and elemental analysis.
  • this layer became stabilized and insoluble.
  • a knife-coating apparatus all other known printing or coating methods such as, for example, spin-coating, slot-die or ink-jet are also possible
  • this layer became stabilized and insoluble.
  • this cross-linking provides for a stabilization and fixation of the geometric structure of the metal complexes, preventing a movement of the ligands and thus a change in structure of the excited molecules and effectively inhibiting a reduction in efficiency due to non-radiative relaxation pathways.
  • the Cu complex (10 mg, 8.13 ⁇ M, 1.0 eq.) shown below was treated with a standard solution of polyglycidyl azide “GAP” in dry dichloromethane (1 mL of a 2440 mg/L solution, 3 eq. azide per eq. complex) and immediately afterwards a thin film produced by spin-coating.
  • the film was stable against rinsing or immersion in toluene.
  • the invention relates in a preferred embodiment to the production of novel optoelectronic inks as emitter materials for organic light-emitting diodes as optoelectronic component.
  • the ink is based on electroluminescent copper(I) complexes, in which diphenylphosphinepyridines, diphenylphosphinechinolines and related heterocycles are used as ligands. These bidentate ligands form polynuclear complexes with copper(I) iodide with a ligand to metal iodide ratio of 3:2.
  • these ligand systems can be substituted with alkyne chains such as 4-butyne and coupled as a copper complex (first reactant with first anchor group) in a click reaction with azides.
  • alkyne chains such as 4-butyne
  • first reactant with first anchor group first reactant with first anchor group
  • azides low-molecular as well as polymeric azides can be converted as a second reactant so that, for example, cross-linked, copper-containing polymers can be synthesized, which combine the electroluminescent properties of the metal complexes with the advantages of the simple liquid processing of the polymers and result in robust, insoluble layers after one baking step.
  • this reaction can be carried out with other ligand classes.
  • further material functions can be implemented into the ink in addition to the cross-linking. Therefore, click-reactions can be used in order to link functional semiconductors (as third reactant), which have hole-transporting or electron-transporting properties, to the complexes.
  • the anchor group e.g. the alkyne linker
  • aromatic azides are used, the emission color of the complexes, which is based on charge-transfer transitions between the metal ions and the ligands, can be influenced.
  • the dimeric complexes each contain three ligands and thus three positions for connection, the complexes can in this way be bound to the polymers as well as bound to hole and electron conductors.
  • the optical, mechanical and electrical properties of the substances obtained that way can for this reason be influenced via the respective composition of the azide mixture.
  • These parameters of the ink can be optimized by robot-supported high-throughput screening methods. With the use of different metal complexes substituted with alkynes, organic light emitting diodes in different colors can be realized, and white-light OLEDS can be achieved by suitable mixture of colors of the corresponding metal complexes.
  • emitters can be linked with an ideal mixture of hole conductors, electron conductors, and a polymer to an optoelectronic ink.
  • the ball shown in 27 stands for polystyrene, but can also represent any other polymer, oligomer or monomer as second reactant.
  • polymeric azides with a polystyrene or polyethylene glycol backbone a cross-linking occurs by complexation.
  • This can be uses by processing: If a freshly produced mixture of the alkyne complex and the azide polymer is applied to a glass substrate by spincoating or knife-coating and the substrate tempered for one hour at 100° C., cross-linked, insoluble layers are formed.
  • thin layers can be produced by means of a wedge-shaped coating knife.
  • the substance is applied in solution onto the substrate and evenly distributed by means of a slide, which can be controlled with a definite gap width and drawing speed.
  • the films thus produced are dried by heating and a nitrogen flow, so that extremely smooth, defined layers can be produced.
  • the polymer dissolved in xylene was mixed in a vial with the metal complex solved in dichloromethane and shortly after mixing was applied as a light cloudy solution to a substrate coated with indium tin oxide (ITO) and PEDOT:PSS. An equimolar stoichiometry was chosen.
  • ITO indium tin oxide
  • PEDOT:PSS PEDOT:PSS
  • the reaction, coating and drying were carried out at various temperatures. Since the whole process was finished after a very short period of time, the samples were subsequently tempered on a heating plate at 100° C. for one hour in order to reach a high yield of the Huisgen reaction. The samples were examined under a UV-lamp as well as by atomic force microscopy. Furthermore, the films were rinsed by immersion in xylene before and after drying for monitoring the reaction. While the cross-linked product is insoluble, the reactants dissolve in this solvent, so that by the resistance of the layers a conclusion about a successful cross-linking can be drawn.
  • the roughness is very low for the measured samples with values between ⁇ 0.53 and 1.64 nm, indicating an excellent morphology of the measured samples.
  • the catalytic potential of the PyrPHOS systems was to be evaluated beyond the Cu(I)-Huisgen reaction.
  • the insoluble, cross-linked PyrPHOS polymers could thus represent a solid-phase catalyst with immobilized Cu(I).
  • the properties of the metal complexes can be modified with such reactions, e.g.:
  • reaction shown above proceeded with complete conversion (determined with IGC-MS). Furthermore, the catalyst that is insoluble in toluene could be filtered off together with the potassium carbonate and remained intact (preservation of the yellow photoluminescence).
  • the product shown on the right side luminesced like the reactant shown on the left.
  • the typical odor of a free thiol was lacking after the reaction.
  • Photoluminescence spectra of the compounds were recorded (powder measurement, room temperature, under normal atmosphere) and are shown in FIG. 5 .
  • the invention also relates to non-copper metal complexes.
  • the anchor groups must be adjusted to the chemical properties of the metal complexes to be linked. For some selected metals, such possibilities are shown in the following examples.
  • Ruthenium complexes also catalyze cycloadditions between alkynes and azides, but result in 1,5-triazoles in contrary to copper-catalyzed click reactions which result in 1,4-triazoles.

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CN103649134A (zh) 2014-03-19
KR102014224B1 (ko) 2019-08-26
CN103649134B (zh) 2016-07-06
US9447246B2 (en) 2016-09-20
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KR20140061390A (ko) 2014-05-21
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KR20140061389A (ko) 2014-05-21
JP6253577B2 (ja) 2017-12-27
EP2729505A2 (fr) 2014-05-14
WO2013007709A2 (fr) 2013-01-17
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CN103649133A (zh) 2014-03-19
WO2013007709A3 (fr) 2013-04-04
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US20140142259A1 (en) 2014-05-22

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